This work aims to determine the roles of reactive oxygen species HO∙ and HO in the bleaching of melanins by alkaline hydrogen peroxide. Experiments using melanosomes isolated from human hair indicated that the HO∙ radical generated in the outside solution does not contribute significantly to bleaching. However, studies using soluble Sepia melanin demonstrated that both HO and HO∙ will individually bleach melanin. Additionally, when both oxidants are present, bleaching is increased dramatically in both rate and extent. Careful experimental design enabled the separation of the roles and effects of these key reactive species, HO∙ and HO. Rationalisation of the results presented, and review of previous literature, allowed the postulation of a simplified general scheme whereby the strong oxidant HO∙ is able to pre-oxidise melanin units to o-quinones enabling more facile ring opening by the more nucleophilic HO. In this manner the efficiency of the roles of both species is maximised.
Globally, billions of individuals wash their hair in water, which acts as an exogenous metal source. Many studies which measure the metal levels found on human hair specifically aim to remove exogenous materials prior to analysis. Although this is needed when using hair analysis to probe the impact of the local environment on endogenous metal levels, it is not relevant for understanding exactly what is on hair as a result of contact with its daily environment. Understanding these levels are important, as the presence of redox active metals, such as copper and iron, can impact fibre health, either as a result of UV irradiation, or during the hair colouring process. A global hair sampling study of over 300 individuals from nine countries has been performed, and the combined endogenous and exogenous metals analysed. The levels measured vary widely, even within the narrow geography of each hair sampling location. The levels of calcium, magnesium, copper and iron were not correlated, and within each location, there are expected to be individuals with high metal levels. Levels increased from hair root to tip for calcium, magnesium and copper, attributed to hair contact with the environment showing the impact of exogenous metals in the overall levels on hair. Levels of redox metals were comparable between individuals who coloured or did not colour their hair, although water hardness ions were statistically significantly higher for hair colouring individuals. Individuals who perceived their hair health as poor had higher metal levels on their hair. Controlling metals on hair, either by preventing their binding during environmental contact, or through controlling their ability to cause hair damage, should lead to improved consumer perceived hair health.
The catalytic formation of hydroxyl radicals in oxidative hair colourant systems in the presence of added copper ions was measured and quantified using a colorimetric probe N,N'-(5-nitro-1,3-phenylene)bisglutaramide. Also monitored in the same experiments was the decomposition of hydrogen peroxide. The first set of experiments was performed using aqueous model solutions containing the key oxidant actives in a hair colourant, ammonium hydroxide and hydrogen peroxide at pH 10, with added copper and calcium ions. The second set of experiments was performed in the presence of hair containing different levels of copper in conditions very close to those found during hair colouring. Both sets of experiments demonstrate the ability of copper ions to trigger the formation of hydroxyl radicals and catalyse the decomposition of hydrogen peroxide. The ability of chelants ethylenediamine tetraacetic acid (EDTA) and N,N'-ethylenediamine disuccinic acid (EDDS) to moderate the flux of hydroxyl radicals formed in solution systems was demonstrated in the presence of copper ions alone. However, only EDDS was successful in the presence of both calcium and copper ions. This was confirmed in the hair experiments where again only EDDS was successful at preventing hydroxyl radical formation where hair is added as the source of copper and calcium ions. These results are explained using metal speciation modelling and demonstrate the importance of the chelant to be able to specifically bind and prevent the one-electron redox chemistry of copper in the presence of high levels of calcium ions as found in hair. The formation of hydroxyl radicals during the colouring process was shown to lead to hair structure damage as measured by protein loss. EDDS was demonstrated to significantly reduce cuticle damage by suppressing the formation of the hydroxyl radicals in systems with realistic concentrations of calcium and copper.
The sorption of aqueous monoethanolamine (MEA) and ammonia solutions in keratin fibers and its subsequent effect on their mechanical performance has been investigated. The diffusion kinetics of MEA into keratin fibers for 0.1, 1.0, and 5 v/v % MEA in water at 30 and 50 °C were found to exhibit two clear regimes of absorption behavior: a linear Fickian diffusion regime for initial times up to 100 min, after which a second slower uptake process was observed. Single fiber tensile tests showed that the Young's modulus and the tensile failure stress for 5% MEA-treated fibers, compared to untreated fibers, were 25% lower after 1 h of treatment and 50% lower after 9 h of treatment. Aqueous treatments of 0.1 and 1% MEA, as well as 0.6 and 3% aqueous ammonia, had no measurable effect on either Young’s modulus or tensile failure stress for the fibers. Scanning electron microscopy images and protein content analysis confirmed that keratin fibers exposed to 5% MEA solution exhibited significant surface damage as well as high levels of protein loss. This study confirms for the first time the important damage hair treatments containing 5% aqueous MEA can cause on keratin fibers.
Hair health is an important attribute to women globally -specifically attributes such as shine, healthy tips, frizz-free and strength. However, many women will claim to have at least moderate hair damage caused by habits and practices such as washing, combing and brushing, use of heated implements and regular use of chemical treatments. The objective of this work was to investigate two mechanisms of damage -hair colouring and UV exposure -where oxidative processes are involved. The role of copper in these oxidative processes was then investigated: its presence in hair and its consequent impact on hair damage via free radical formation. Finally, the role of chelants N,N'-ethylene diamine disuccinic acid (EDDS) and histidine in preventing free radical formation was investigated and shown to improve hair health. R esum eLa sant e des leurs cheveux est un sujet important pour les femmes dans le monde entier -en particulier les attributs sp ecifiques de brillance, absence de frisottis et pointes en bonne sant e. Cependant, beaucoup de femmes affirment avoir au moins quelques probl emes de cheveux caus es par leurs habitudes et leurs pratiques de lavage, peignage, brossage, utilisation d'outils chauffants et de traitements chimiques. L'objectif de ce travail etait d' etudier deux m ecanismes d'agression -la coloration des cheveux et l'exposition aux UVdans lesquels des processus d'oxydation sont impliqu es. Le rôle du cuivre dans ces processus oxydatifs a ensuite et e etudi e; sa pr esence dans les cheveux et son incidence sur les dommages des cheveux par la formation de radicaux libres. Enfin, le rôle des agents ch elateurs comme l'acide N-ethyl ene diamine di-succinique et l'histidine a pr evenir la formation de radicaux libres a et e etudi e et leur efficacit e a am eliorer la sante des cheveux a et e d emontr ee.
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